1,3-Benzodithiole tetraoxide as a CH22- synthon

Kündig, E. Peter; Cunningham, Allan F.

doi:10.1016/s0040-4020(01)86213-x

Cited by 50 publications

(33 citation statements)

References 14 publications

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“…The latter can be prepared by the method of Kündig [6] and 3 by simple oxidation of the corresponding bisA C H T U N G T R E N N U N G (sulphide) with meta-chloroperbenzoic acid (mCPBA). The viability of the proposal was first assessed for basecatalyzed conjugate addition reactions, by using a selection of prototypical Michael acceptors and gem-bisA C H T U N G T R E N N U N G (sulfone)s 1-5.…”

Section: Resultsmentioning

confidence: 99%

“…However, this sulfone proved to be resistant towards the 1,4-addition reaction under a variety of conditions. Alternatively, it was found that the a-alkylation of either bisA C H T U N G T R E N N U N G (sulfone) adducts 13 or 14 with both reactive and less reactive long chain alkyl halides, according to the procedure of Kündig, [6] is feasible (Scheme 6). Thus, a convenient and stereocontrolled access to products bearing alkyl side chains other than methyl is provided, as exemplified by protected alcohol products 26-28 and aldehydes 30 and 31.…”

Section: Resultsmentioning

confidence: 99%

“…[22] 1,3-Benzodithiole tetraoxide 4 was prepared according to a published procedure. [6] Benzylideneacetone, Et 3 N, DBU, pyrrolidine, guanidines TBD/MTBD, and catalysts 8, 9, 10, and 11 were purchased from Aldrich and used as supplied. For the preparation of compounds 19 and 22, see the Supporting Information.…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Catalytic Conjugate Additions of Geminal Bis(sulfone)s: Expanding the Chemistry of Sulfones as Simple Alkyl Anion Equivalents

Landa

Puente

Santos

et al. 2009

Chemistry A European J

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The value of cyclic gem-bis(sulfone) 4 as a simple alkyl nucleophile equivalent in catalytic C-C bond-forming reactions is demonstrated. The 1,4-type nucleophilic additions of bis(sulfone) 4 to alpha,beta-unsaturated ketones take place by assistance of catalytic guanidine base. On the other hand, pyrrolidines are able to catalyze the conjugate addition of 4 to both enones and enals, likely by means of iminium ion activation. Upon exploration of the best chiral pyrrolidine catalyst, it has been found that the addition of 4 to enals catalyzed by diphenylprolinol silyl ether 10 proceeds with very high enantioselectivity (beta-aryl-substituted enals >95% ee; beta-alkyl substituted enals up to 94% ee; ee = enantiomeric excess). Further reductive desulfonation of adducts gives rise to the corresponding beta-methyl aldehydes, as well as the derived alcohols, acetals, and methyl esters after simple (Mg, MeOH) well-established protocols. Application of the procedure to the synthesis of biologically relevant phenethyl building blocks is shown. Most interestingly, alpha-alkylation of initially obtained bis(sulfone) adducts can be done even with less reactive alkylating reagents, such as long linear-chain or branched-chain alkyl halides. Accordingly, upon the desulfonation process, a general, experimentally simple and highly enantioselective access to beta-branched aldehydes, alcohols, or esters is possible. Further exploration of the method includes the use of chiral alpha,beta-unsaturated aldehydes derived from citronellal as the Michael acceptor partners. In these instances, the sense of the conjugate addition of 4 is controlled by the chirality of the pyrrolidine catalyst, thus allowing for a stereochemically predictable access to 1,3-dimethyl arrays, such as those present in deoxygenated polyketide-type natural products. The intramolecular variation of this technology by using doubly unsaturated aldehyde-ester 22 illustrated the site selectivity of the procedure and its potential for tandem processes leading to highly substituted polycyclic systems, such as 24.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Catalytic Conjugate Additions of Geminal Bis(sulfone)s: Expanding the Chemistry of Sulfones as Simple Alkyl Anion Equivalents

Landa

Puente

Santos

et al. 2009

Chemistry A European J

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“…Other such anions, such as 2-lithio-1,3-benzodithioles (1 Li , Scheme 1), have also been recommended as masked acyl anions. 4,5 In addition to reversing the carbonyl group reactivity, anions from 1,3-dithioles are also very useful as building blocks for new sulfur heterocycles. Researchers have investigated 6,7 the reactions of these species with CS 2 as a way to an interesting synthon and a redox-active ligand (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Specific Reactivity of Isomeric 1,3-Benzodithiole Anions: Tandem Mass Spectrometry and DFT Theoretical Studies

et al. 2001

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1,3-Benzodithiole dideuterated at the dithioacetal carbon atom has been ionized in the chemical ionization source of a tandem triple quadrupole mass spectrometer under NICI condition. Two isomeric anions are formed by abstraction of an o-phenylic proton or through abstraction of a deuteron. The fragmentation patterns occurring under dissociative collisions differ and confirm the coexistence of two nonconverting carbanions. DFT calculations show that the dithioacetal anion is more stable than the phenylic. The nucleophilic reactivity toward CS 2 has been studied by collision-induced reactions in the collision cell of the tandem instrument. Both isomeric anion forms display characteristic fragmentations of the resulting [(M-H(D)) + CS 2 ] adduct anions, demonstrating a difference in reactivity: the dithioacetal anion reacts regioselectively at C and the o-phenylic at S. DFT calculations, performed with the aim of rationalizing this observed difference and understanding the formation of the diagnostic fragments, have been successful.

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“…[1][2][3][4] Moreover, some of them (sulfonal, trional, and tetronal) are classical sedative-hypnotics 5) ( Fig. 1).…”

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confidence: 99%

Niobium(V) Chloride Catalyzed Oxidation of Dithioacetals with 30% Hydrogen Peroxide: A Concise Preparation of Bissulfonylmethylene Compounds

Kirihara

Goto

Noguchi

et al. 2013

CHEMICAL & PHARMACEUTICAL BULLETIN

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1,3-Benzodithiole tetraoxide as a CH22- synthon

Cited by 50 publications

References 14 publications

Catalytic Conjugate Additions of Geminal Bis(sulfone)s: Expanding the Chemistry of Sulfones as Simple Alkyl Anion Equivalents

Catalytic Conjugate Additions of Geminal Bis(sulfone)s: Expanding the Chemistry of Sulfones as Simple Alkyl Anion Equivalents

Gas-Phase Specific Reactivity of Isomeric 1,3-Benzodithiole Anions: Tandem Mass Spectrometry and DFT Theoretical Studies

Niobium(V) Chloride Catalyzed Oxidation of Dithioacetals with 30% Hydrogen Peroxide: A Concise Preparation of Bissulfonylmethylene Compounds

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